Bis-iminopyrrolines



United States Patent C) 2,975,189 BIs I Y msmE-s Newman M. Bortnick, OreIand, and Marian F. Fegley,

Mont Clare, Pa.,' as'sign'ors to Rohm & Haas Company, Bhiladelphia, Pa., a corporation of Delaware N9 Ta'lY -P F le M 195. 8 NQ- .1 2 93 14 Claims. or. 259-313 in a molecular ratio of substantially two. oi the former to] one of the. latter; to, be: more ully'explained, hereinagitei." The bisI-inunOPYIIQHfles produced may be represented the formula. '4

Actually, the compound represented by Formula I is in varying degrees depending principally on reaction conditions and the values of; A, R R R and R in tautomeric relationship with the compounds having the following structures It s. h a h p ed mi an a qms isn s st is that represented by Formula I but appreciable amounts o v II, III, and IV are undoubtedly present, based on. the bestexperimental and, analytical evidence. Inthe pres; ent. instance, Formula I. will be referred. toas thermost probably form of. the. four: possible. tautomeric structures (B 1 and; V) b ssh. efe e ce is. meantto in.- clude all; four of the tautorneric forms,

e ysibsllh ep se t hY r a b sasvRss a to ten. carbon atoms, preferably alkyl, ara ll ryl, cyclo;

styli ts-i1, 'sidi' ls ssq ibslial stssset l 2,975,189 Patented Mar. 14, 136.1

hydrogen atom or an allgyl group oi one to four carbon atoms. The symbols R and R may be hydrogen atoms or hydrocarbon groups containing from one to ten carbon atoms including alkyl, aralkyl, cycloalkyl, ary-l, and alkaryl groups. In addition, R and R taken together with the carbon atoms to which they are joined may form a carbocyclic ring containing five to six carbon atoms which in turn may have alkyl substituents containing a total of no more than fouradditional carbon atoms. In addition, R and R taken together with the carbon atoms to which they are joined may form a carbocyclic ring containing five to six carbon atoms which in turn may I have alkyl substituents containing a total ofno more than four additional carbon atoms. In addition, R and R taken together with the carbon atoms to which they are joined may form a carbocyclic ring containing five to six carbon atoms which ins-turn may have alkyl substituents containing a total of no more than four additional carbon atoms. The total number of carbon atoms in the cyanoketone should not exceed twenty-four. The preferred embodiments are those in which R and R are alkyl groups, R is a hydrogen atom, and R is a methyl group. R R and K; may typically individually represent methyl, butyl, octyl, ben z yl, phenylbutyl, cyclopentyl, cyclohexyl, .phenyl, naphthyl, butylphenyl groups,

and the like.

Typical cyanoketone reactants include 4-oxopentanonitrile, 3-methyl-4-oxopentanonitrile, 2,2-dimethyl-4-oxopentanonitrile, 2-methy1-2-ethyl-4-oxopentanonitrile,

- 2,4,8-trimethyl-4-cyano-6-nonanone,

2-methyl 2 (2,2,4,4-tetramethylpentyl)-4-oxopentanonitrile, 2-methyl-Z-ethyl-4-oxoheptanonitrile, 2emethyl-2-hexyl-4-oxodecanonitrile, 2-isobutyl-2,6-dimethyl-4-oxoheptanonitrile, 2-methyl-2-neopentyl;4;oxopentanonitrile, 2-methyl-2,4-diphenyl-4-oxobutanonitrile, 2-( l-cyanocyclohexyl -cyclohexanone, 2-methyl2,4-dicyclohexyl-4-oxobutanonitrile, i-m@t;h -2:( rm hy r y s y e n e, 1,3,3-trimethyl-5-oxocyclohexane-carbonitrile, z acetyl-l methylcyclopentanecarbonitrile, -bu lrlthYlroxsqyslop ma s ev L-fii-sxmwlspsntat) sy lohs e rbs ri e,, it wean- QQ W )r Y l Pfin a fl a b niir fii. l ssztx i tbs t gaoeyqlo ex n cat s t ei. 3, i etha (Z-easem nt) rbisys oml- 1:] hsptane-lr.

carbonitrile, 2-benzoyl-1-methylcyclopentanecarbonitrile, and 2-butyl-2-naphthyl-4-oxobutanonitrile.

The symbol A represents a chain, cyclic or acyclic, of at least four carbon atoms, A is usually hydrocarbon in a ies bassistat s i n l sis a s t s st asr mine, g oan, a ether oxyge at ne;- i sthe l l ta s. W he ke. W it h u as mi s wsr a atoms in A is not especially critical about 24.; is con; ids sd; he. P s issl nest imit: n ad ss 5 ar stilsi h rstm' y s-Q ssr ars nitrsg q w u t l em s ss nt. a P ou l -m n d Wi h t sasdfislhs sssst at NEVA-Wa is s s s r hat there be, at least four carbon atoms between the; two,

primary amino groups. is also necessarythat each he P imary. in s b acheda s r nz qm hat; n t r tt s i to 1 mots han; t ca b n.

ste s. aws hs srdsi s. s hnat a h sh sash ofthe. primary amino, groups is attached mu stmear at lea 2 h dr en om o h rw se he; ea ies. siqat.

ssn wams sslia -ah h g s sss f ats s ina s ie sss i issst. 1 s 1 arm-@mn N Hz-QN H:

CHQNH:

CH3 C H! NHzCH C HiNH:

CHzNHa NHaCHr-CHnNHa NHrQ-CHQNH;

NHzCHr The reactants of this invention are compounds that are known or prepared by known methods.

It has been previously stated that the product of this invention is a specific bis-iminopyrroline having the Formula I. However, if the reactants of this invention are mixed and allowed to stand at room temperature or at temperatures up to about 75 C. over prolonged periods of time, a product is formed having the formula and The Formula V compounds are usually crystalline solids which, when heated to a range approaching that required for distillation, lose water and are converted to a Formula I product.

The Formula I compounds, and these of course encompass types II, III, and IV, as discussed heretofore, are predominantly formed under conditions whereby water as formed in the reaction is removed from the reaction medium. The preferred method is to conduct the reaction in the presence of an inert volatile organic solvent that forms an azeotrope with water. Useful as a solvent in this respect are benzene, toluene, xylene, heptane, hexane, methylene, chloride, chloroform, and the like. The water is removed azeotropically as the reaction progresses, preferably at about 40 C. to 250 C., and very little, if any, of the type V product is formed. The reaction is desirably terminated when the substan- 4 tially theoretical amount of water is removed. The product may be isolated by distillation under reduced pressure or recrystallization from a solvent, such as isooctane, as desired. If the diprimary amino reactant has been used in excess it has to be separated from the product at the conclusion of the reaction, by conventional methods, or otherwise a diprimary amino addition salt will form.

It is probable that in some instances mixtures of products are obtained but this is no deterrent to the present invention. The compounds of this invention, whether of the types corresponding to I or V or mixtures thereof, are valuable for the present purposes. The present compounds are useful as fungicides which are non-injurious to plants upon which they are applied.

These compounds effectively control Monilinia fracticola and Stemphylium sarcinaeforme when used according to standard techniques in concentrations as low as one to ten parts per million. At the same time the present compounds are non-phytotoxic even in concentrations as high as one-hundred parts per million. Particularly eflective in this respect are l,7-bis(2,4,4-trimethyl-2-pyrrolin-5-ylidene)-1,4,7-triazaheptane and 1,8- bis(2,4,4-trimethyl-2-pyrrolin-5-ylidene)-l,8-diazaoctane.

The compounds of this invention, as well as the methods for their preparation, may be more fully understood from the following examples which are offered by way of illustration and not by way of limitation. Parts by weight are used throughout.

Example 1 Hexamethylenediamine (41 parts of an aqueous 75% solution), and toluene (35 parts) are placed in a boiling flask topped by a water separating head and reflux condenser. Toluene (25 parts) is placed in the water separator initially. The reaction mixture is boiled under reflux in order to separate water azeotropically. Water (11 parts) is removed in the course of this preliminary drying operation. There is added 2,2-dimethyl-4-oxopentanonitrile (62.5 parts) when the water separation is completed. Again the mixture is heated to reflux and water is removed azeotropically. The pot temperature remains in the region 154-160 C., under which conditions the theoretical amount of water (9 parts) separates. The reaction mixture is stripped of low-boiling materials to a pot temperature of C. at 0.2 mm. absolute pressure. The residue (81 parts) is the desired product, 1,8- bis( 2,4,4 trimethyl-2-pyrrolin-5-ylidene)-l,8-diazaoctane having the formula CH3 CH3 1'1 lit Calculated for C H N total nitrogen-17.0%; titratable nitrogen-8.5%. Found: total nitrogen- 16.5%; titratable nitrogen--8.3%.

The yield is 98% of the theoretical.

In the same manner, hexamethylenediamine and 2- methyl-2-neopentyl-4-oxopentanonitrile give 1,8-bis(2,4 dimethyl 4 neopentyl 2 pyrrolin 5 ylidene)-l,8- diazaoctane; 1,5 pentarnethylenediamine and l-(2-oxocyclohexyl) 1 cyclohexanecarbonitrile give 1,7-bis(3,3- pentamethylene 2,3,4,5,6,7 hexahydroindol-2-ylidene)- 1,7 diazaheptane; hexamethylenediamine and 2,6 dimethyl 2-(2-methylpropyl) 4 oxoheptanonitrile give 1,8 bis[4 methyl 2,4 di(2-methylpropyl) 2 pyrrolin 5 ylidene]-1,8 diazaoctane; 1,4 diaminocyclohexane and 2,2-dimethyl-4-oxopentanonitrile give N,N'- bis-(2,4,4-trimethyl 2 pyrrolin 5 ylidene) 1,4-diaminocyclohexane; m-xylenylenediamine and 2,2dimethyl-4-oxopentanonitrile give N,N'-bis-(2,4,4-trimethyl-2- pyrrolin-S-ylidene)-m-xylenylenediamine; and p-phenylenediamine and a,ot,4 trirnethyl 2 oxocyclohexane- Diethylenetriamine (72 parts), 2,2-dimethy1 4 oxopentanonitrile (125 parts), and benzene (40 parts) are charged to'a reactor fitted with a water separator and capped by a reflux condenser. The reaction mixture is boiled under reflux and water is separated azeotropically; When the theoretical amount of water (18 parts) separates, the material is stripped under reduced pressure and finally to 90 C. at 0.1 'mmfab'solute pressure.

Calculated for C H N total nitrogen22.0%; titratable nitrogen-13.2%.' Found: total nitrogen21.2%; titratable nitrogen-12.1%.

The product is 1,7-bis(2,4,4 trimethyl-Z-pyrrolin-S- ylidene) -l,4,7-triazaheptane and has the following structure In a similar fashion 1,5,8,l2-tetrazadodecane and 2,2- dimethyl 4 oxopentanonitrile give l,l2-bis'(2,4,4-"trimethyl 2 pyrrolin 5 -y1ider 1e) 1,5,8,12 tetrazadodecane; 1,9 diaza 5 oxanona'ne and l-(2-oxocyclohe xyl) 'cyclohexanecarbonitrile give 1,9 bis(3,3-penta methylene 2,3,4,5,6,7 hexahydroindol 2 ylidene} 1,9 diaza 5'-'oxanonane; 1,9 diaminodiaza -5' -'thianonane and 2 acetyl"-' cyclohexanecarbonitril'e give 1,9'- bis(3 methyl 2,4,5,6,7,7a he'xahydroisoindol 1- yliden'e) 1,9 diaza- 5 thianonanet and 1,15 "-diaza- S- Xapentadecane and 3methyl-4-oxapentanonitrile"give 1,15-bis(2,3-'dime'thyl 2 -pyrrolin 1 5 ylidene) 1,15- diaza-8 oxapentade'cane' Example 3 Xylene (30 parts), 1,10-diaminodecane (17.2 parts), and Z-methyl 2,4 diphenyl 4 oxobutanonitrile (50 parts) are refluxed for twenty-four hours until the theoretical amount of water (3.6 parts) separates. The reaction mixture is strippedunder reduced pressure to give the product 1,12 bis(4 methyl 2,4 diphenyl, 2 pyrrolin-5-ylidene)-1,12-diazadodecane, in high yield. In a similar fashion there are prepared N,N'-bis(3,3-p'e'ntamethylene 2,3,4,5,6,7 hexahydroindol 2 ylidene)- 2,5 diaminpbicyclo(2.2.1)heptane from l (2-oxocyclohexyl) cycloheiianeca rbonitrile and 2,5-diaminobicyclo (2.2.1)heptane; N,N bis(4 methyl 2,4 dihexyl 2- pyrrolin 5 ylidene) 1,4-di(aminomethyl) cyclohexane from l,4-di(aminomethyl-cyclohexane and 2 methyl- 2-hexyl-4-oxodecanonitrile; and 1,10-bis(2,4,4-trimethyl- 2 pyrrolin 5 ylidene) 1,4,7,1O tetrazadecane from triethylenetetrarnine and 2,2-dimethyl 4 oxopentanonitrile. e

We claim:

1. A member from the group consisting of the compound whose principal tautomeric form is represented by the formula and the pharmaceutically acceptable acid addition salts thereof, in which A represents a member of 4 to 24 carbon atoms from the group consisting of alkylene, cycloalkylene, phenylene, alkylene phenylenealkylene, alkylenealkyl substituted phenylenealkylene, phenylenealkylene, alkylenecycloalkylenealkylene, bicycloalkylene, and an 'alkylene interrupted by at least one member of the class consisting of an amino group, an alkylaminogroup,

an ether oxygen atom, and a thioether sulfur atom, provide'dthat there are at least 2 carbon atoms between the members of said class, R taken individually represents amember from the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naphthyl, and alkylphenyl groups of no more than 10 carbon atoms, R taken individually represents a member from the class consisting of a hydrogen atom and an alkyl group of 1 to 4 carbon atoms, R and R taken individually represent members from the class consisting of alkyl, cycloalkyl, phenylalkyl, phenyl,

naphthyl, and alkylphenyl groups of no more than 10 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a member from the class consisting of a carbocyclic ring of 5 to 6 carbon atoms and one olefinic bond, and said ring having alkyl substituents consisting of a total of no more than 4 carbon atoms, R and R taken collectively with the carbon atoms to which they. are joined from a memher from the class consisting of a saturated carbocyclic ring of '5 to 6 carbon atoms and said ring having alkyl substituents consisting of a total of no more than 4 carbon atoms, and R and R taken collectively with the carbon atoms to which theyv are, joined from a member from the class consisting of a saturated carbocyclic ring of S to 6 carbon atoms'and said ring having alkyl substituents consisting of a total of no more than 4 carbon atoms.

'2. The compound whose principal tautomeric form is represented by the formula R3 R -R4] R1 =N A in which A represents an alkylene chain of. 4 to 24 carbon I atoms, R and R; are alkyl groups oil to' lO'carb'oii atoms, R is a hydrogen atom, and R is a methyl group; 4. The compound whose principal tautomeric form is represented by the formula in which A represents an alkylene chain of 4 to 24 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined represent a'carbocyclic ring. of 5 to 6 carbon atoms having one olefinic bond and R and R are alkyl groups of 1 to 10 carbon atoms. 7

5. The compound whose principal tautomeric form is represented by the formula Ra, R3- R4] R1 N =N TA.

in which A represents an alkylene chain of 4 to 24 carbon atoms, R is an alkyl group of 1 to 10 carbon atoms, R; and R taken collectively with the carbon atoms to which they are joined form a saturated carbocyclic ring of to 6 carbon atoms and R is an alkyl group of 1 to carbon atoms.

6. The compound Whose principal tautomeric form is represented by the formula in which A represents an alkylene chain of 4 to 24 carbon atoms, R, is an alkyl group of 1 to 10 carbon atoms, R is an alkyl group of 1 to 4 carbon atoms and R and R taken collectively with the carbon atoms to which they are joined form a saturated carbocyclic ring of 5 to 6 carbon atoms.

7. As a composition of matter, 1,8-bis(2,4,4-trimethyl- 2-pyrrolin-5-ylidene)-1,8-diazaoctane.

8. As a composition of matter, 1,8-bis(2,4-dimethyl- 4-neopentyl-2-pyrrolin-5-ylidene)-1,8-diazaoctane.

9. As a composition of matter, 1,7-bis(3,3-pentamethylene-2,3,4,5,6,7-heXahydroindol-Z-ylidene)-1,4,7-triazaheptane.

10. As a composition of matter, 1,7-bis(2,4,4-trimethyl- 2-pyrrolin-5-ylidene) -1,4,7-triazaheptane.

11. As a composition of matter, 1,12-bis(2,4,4-trimethyl-2-pyrrolin-5-ylidene)4,5,8,12-tetraazadodecane.

12. A method for the preparation of a compound having the formula in which A represents a member of 4 to 24 carbon atoms from the group consisting of alkylene, cycloalkylene, phenylene, alkylenephenylenealkylene, alkylenealkyl substituted phenylenealkylene, phenylenealkylene, alkylenecycloalkylenealkylene, bicycloalkylene, and an alkylene interrupted by at least one member of the class consisting of an amino group, an alkylamino group, and an ether oxygen atom, and a thioether sulfur atom, provided that there are at least 2 carbon atoms between the members of said class, R taken individually represents a member from the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naphthyl, and alkylphenyl groups of no more than 10 carbon atoms, R taken individually represents a member from the class consisting of a hydrogen atom and an alkyl group of 1 to 4 carbon atoms, R, and R taken individually represent members from the class consisting of alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and alkylphenyl groups of no more than 10 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a member from the class consisting of a carbocyclic ring of 5 to 6 carbon atoms and one olefinic bond, and said ring having alkyl substituents consisting of a total of no more than 4 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a mem her from the class consisting of a saturated carbocyclic ring of 5 to 6 carbon atoms and said ring having alkyl substituents consisting of a total of no more than 4 carbon atoms, and R and R taken collectively with the carbon atoms to which they are joined form a member from the class consisting of a saturated carbocyclic ring of 5 to 6 carbon atoms and said ring having alkyl substituents consisting of a total of no more than 4 carbon atoms, which comprises reacting at temperatures from 40 to 250 C., a compound having the formula R R3 R1CCH(IIR4 with one having the formula in which there are at least 4 carbon atoms between the two primary amino groups and in which each of the primary amino groups is attached to a carbon atom that bears at least one hydrogen atom.

13. A method according to claim 12 in which the reaction is conducted in the presence of an inert volatile organic solvent that forms an azeotrope with water.

14. A method according to claim 12 in which the reaction is conducted in the presence of an inert organic volatile solvent that forms an azeotrope with water and the water formed in the reaction is removed azeotropically as the reaction progresses.

References Cited in the file of this patent UNITED STATES PATENTS 2,417,046 Brooks et al. Mar. 11, 1947 2,469,830 Knott May 10, 1949 2,580,738 De Benneville Jan. 1, 1952 FOREIGN PATENTS 669,037 Germany Nov. 25, 1940 

1. A MEMBER FROM THE GROUP CONSISTING OF THE COMPOUND WHOSE PRINCIPAL TAUTOMERIC FORM IS REPRESENTED BY THE FORMULA 